Heterogeneous and Homogeneous Catalytic Oxidation by Supported γ-FeOOH in a Fluidized-Bed Reactor:  Kinetic Approach

Oxidation of benzoic acid (BA) by H2O2 was performed with a novel supported γ-FeOOH catalyst in a circulating fluidized-bed reactor (CFBR). This study focused mainly on determining the proportions of homogeneous catalysis and heterogeneous catalysis in this CFBR. Also studied herein was how pH, H2O2 concentration, and BA concentration affect the oxidation of BA. Experimental results indicate that the decomposition rate of H2O2 was proportional to its concentration and that the oxidation rate of BA depended on both H2O2 and BA concentrations. The change in the rate constant of heterogeneous catalysis by pH was described in terms of ionization fractions of surface hydroxyl group. From the mathematical deduction, we can infer that the reaction rate associated with ⋮FeIIIOH2 + is markedly higher than that with ⋮FeIIIOH. Conclusively, although heterogeneous catalysis contributes primarily to the oxidation of BA at pH 4.4−7.0, the homogeneous catalysis is of increasing importance below pH 4.4 because of the reductive dissolution of γ-FeOOH.